Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes
Nanoscale control of chemical reactivity, manipulation of reaction pathways, and ultimately driving the outcome of chemical reactions are quickly becoming reality. A variety of tools are concurring to establish such capability. The confinement of guest molecules inside nanoreactors, such as the holl...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-12-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/13/1/8 |
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| author | Tainah Dorina Marforio Michele Tomasini Andrea Bottoni Francesco Zerbetto Edoardo Jun Mattioli Matteo Calvaresi |
| author_facet | Tainah Dorina Marforio Michele Tomasini Andrea Bottoni Francesco Zerbetto Edoardo Jun Mattioli Matteo Calvaresi |
| author_sort | Tainah Dorina Marforio |
| collection | DOAJ |
| description | Nanoscale control of chemical reactivity, manipulation of reaction pathways, and ultimately driving the outcome of chemical reactions are quickly becoming reality. A variety of tools are concurring to establish such capability. The confinement of guest molecules inside nanoreactors, such as the hollow nanostructures of carbon nanotubes (CNTs), is a straightforward and highly fascinating approach. It mechanically hinders some molecular movements but also decreases the free energy of translation of the system with respect to that of a macroscopic solution. Here, we examined, at the quantum mechanics/molecular mechanics (QM/MM) level, the effect of confinement inside CNTs on nucleophilic substitution (S<sub>N</sub>2) and elimination (<i>syn</i>-E2 and <i>anti</i>-E2) using as a model system the reaction between ethyl chloride and chloride. Our results show that the three reaction mechanisms are kinetically and thermodynamically affected by the CNT host. The size of the nanoreactor, i.e., the CNT diameter, represents the key factor to control the energy profiles of the reactions. A careful analysis of the interactions between the CNTs and the reactive system allowed us to identify the driving force of the catalytic process. The electrostatic term controls the reaction kinetics in the S<sub>N</sub>2 and <i>syn</i>/<i>anti</i>-E2 reactions. The van der Waals interactions play an important role in the stabilization of the product of the elimination process. |
| first_indexed | 2024-03-09T09:43:21Z |
| format | Article |
| id | doaj.art-17ad619d71db44779821fdf3a3140b63 |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-09T09:43:21Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-17ad619d71db44779821fdf3a3140b632023-12-02T00:43:38ZengMDPI AGNanomaterials2079-49912022-12-01131810.3390/nano13010008Deciphering the Reactive Pathways of Competitive Reactions inside Carbon NanotubesTainah Dorina Marforio0Michele Tomasini1Andrea Bottoni2Francesco Zerbetto3Edoardo Jun Mattioli4Matteo Calvaresi5Dipartimento di Chimica “Giacomo Ciamician”, Alma Mater Studiorum-Università di Bologna, Via Francesco Selmi 2, 40126 Bologna, ItalyDipartimento di Chimica “Giacomo Ciamician”, Alma Mater Studiorum-Università di Bologna, Via Francesco Selmi 2, 40126 Bologna, ItalyDipartimento di Chimica “Giacomo Ciamician”, Alma Mater Studiorum-Università di Bologna, Via Francesco Selmi 2, 40126 Bologna, ItalyDipartimento di Chimica “Giacomo Ciamician”, Alma Mater Studiorum-Università di Bologna, Via Francesco Selmi 2, 40126 Bologna, ItalyDipartimento di Chimica “Giacomo Ciamician”, Alma Mater Studiorum-Università di Bologna, Via Francesco Selmi 2, 40126 Bologna, ItalyDipartimento di Chimica “Giacomo Ciamician”, Alma Mater Studiorum-Università di Bologna, Via Francesco Selmi 2, 40126 Bologna, ItalyNanoscale control of chemical reactivity, manipulation of reaction pathways, and ultimately driving the outcome of chemical reactions are quickly becoming reality. A variety of tools are concurring to establish such capability. The confinement of guest molecules inside nanoreactors, such as the hollow nanostructures of carbon nanotubes (CNTs), is a straightforward and highly fascinating approach. It mechanically hinders some molecular movements but also decreases the free energy of translation of the system with respect to that of a macroscopic solution. Here, we examined, at the quantum mechanics/molecular mechanics (QM/MM) level, the effect of confinement inside CNTs on nucleophilic substitution (S<sub>N</sub>2) and elimination (<i>syn</i>-E2 and <i>anti</i>-E2) using as a model system the reaction between ethyl chloride and chloride. Our results show that the three reaction mechanisms are kinetically and thermodynamically affected by the CNT host. The size of the nanoreactor, i.e., the CNT diameter, represents the key factor to control the energy profiles of the reactions. A careful analysis of the interactions between the CNTs and the reactive system allowed us to identify the driving force of the catalytic process. The electrostatic term controls the reaction kinetics in the S<sub>N</sub>2 and <i>syn</i>/<i>anti</i>-E2 reactions. The van der Waals interactions play an important role in the stabilization of the product of the elimination process.https://www.mdpi.com/2079-4991/13/1/8nanoreactorscarbon nanotubesnanoconfinementnucleophilic substitution S<sub>N</sub>2elimination reaction E2catalysis |
| spellingShingle | Tainah Dorina Marforio Michele Tomasini Andrea Bottoni Francesco Zerbetto Edoardo Jun Mattioli Matteo Calvaresi Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes Nanomaterials nanoreactors carbon nanotubes nanoconfinement nucleophilic substitution S<sub>N</sub>2 elimination reaction E2 catalysis |
| title | Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes |
| title_full | Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes |
| title_fullStr | Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes |
| title_full_unstemmed | Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes |
| title_short | Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes |
| title_sort | deciphering the reactive pathways of competitive reactions inside carbon nanotubes |
| topic | nanoreactors carbon nanotubes nanoconfinement nucleophilic substitution S<sub>N</sub>2 elimination reaction E2 catalysis |
| url | https://www.mdpi.com/2079-4991/13/1/8 |
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